【作者】 屠春来；

【导师】 舒谋海；

【作者基本信息】 上海交通大学 ， 应用化学， 2007， 硕士

【摘要】 通过人工合成的分子反应器模拟细胞空腔及酶的催化功能是当前国际化学研究的一个新的前沿领域。本文通过定向合成及自组装的方法对新型分子反应器的合成及性质进行了一些探索性的研究,主要取得以下成果。(1)合成了1,3,5-三吡唑苯和1,3,5-三(对吡唑苯基)苯两个三齿配体,并与硝酸银、高氯酸银自组装得到微孔聚合物反应器{[Ag3L32(ClO4)2]ClO4}n和{[Ag3L32(NO3)2]NO3}n,通过单晶X射线衍射、粉末X射线衍射、红外光谱、固体荧光光谱和原子吸收等测试方法对化合物进行了表征,研究表明孔道中的自由阴离子具有离子交换性质,配合物的形成对配体的荧光性能产生影响。(2)从对叔丁基苯酚为起始原料合成了下沿选择性修饰的杯[6]芳烃,再与以2,6-二羧酸吡啶甲酯为原料合成的三脚架穴状配体进行1+1的环化反应,得到两个C3v-对称的分子反应器主体分子L1和L2,用电喷雾质谱、单晶X射线衍射和核磁共振等多种测试方法对它们的结构进行了表征,用1H NMR研究了L1对客体分子的选择性识别行为,发现其对直链有机小分子胺具有可控的可逆的识别功能。(3)通过对α-环糊精进行了选择性修饰,合成了以α-环糊精为主体空腔的新的含氮配体。更多还原

【Abstract】 It’s a new topic for chemists to research on modeling the function of cell’s environment and enzymes via synthesis artificial molecular reactors. This work introduced several new molecular reactors obtained by directional synthesis and the self-assembly method, and pilot studies of their properties. The major work was focused on three aspects as follows: (1) Two new C3v-symmetrical molecular reactors L1 and L2 based on calix[6]arene were synthesized by Calix[6]arene with the low rims modified and tripodal cavity ligand which were made from 4-tert-butylphenol and dimethyl pyridine-2,6- dicarboxylate, respectively, in [1+1] macrocyclization reaction, and characterized by ES-MS, single crystal X-ray diffraction, and nuclear magnetic resonance. Further more, some researches were carried out on the selective recognition of L1with guest molecules by 1H NMR, and the results indicated that L1 can controllably recognize small straight chain ammoniums reversibly. (2) 1,3,5-tris(pyrazol-1-yl)benzene and 1,3,5-tris [p-(pyrazol-1-yl)phenyl]benzene were synthesized, and porous polymer reactors {[Ag3L32(ClO4)2]ClO4}n and {[Ag3L32(NO3)2]NO3}n were obtained by self-assembly of L3 with silver nitrate and silver perchlorate. The structures and properties were characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR, photoluminescence and atomic absorption spectra. The free anions in porous channels can be exchanged reversibly. The photoluminescent property of L4 can be influenced by formation of silver complex. (3) A novel chiral reactor based onα-cyclodextrin that was modified selectively has been prepared.更多还原